High energy polymers formed by ring opening metathesis polymerization

Abstract

A precursor route to the synthesis of polyacetylene and other conductive polymers is provided by the formation of high energy polymers by ring opening metathesis polymerization. In particular, the high energy polymers having the following general formula are formed from monomers as shown: ##STR1## In the formula, A is an organic structure that is relieved of strain upon the ring opening polymerization and B is an organic structure with strain energy≧20 kcal/mole. Such high energy polymers are also found to be spontaneously decomposable with heat or mechanical stress. Consequently, the high energy polymers formed in accordance with the invention may find use in explosives or other sources of high energy.

What is claimed is: 
     
       1. A process for forming a high energy polymer comprising subjecting monomer to a ring opening metathesis polymerization in the presence of a non-Lewis acidic tungsten alkylidene metathesis catalyst to form said high energy polymer, wherein said monomer and said polymer are selected from the group consisting of ##STR9## where R is an alkyl and n ranges from about 8 to 7,700. 
     
     
       2. The process of claim 1 wherein said catalyst has the formula (RO) 2  W(N(2,6-diisopropylphenyl))CHC(CH 3 ) 3 , wherein R=t-butyl or hexafluoro-t-butyl. 
     
     
       3. Product produced by the process of claim 1. 
     
     
       4. A process for forming polybenzvalene comprising subjecting benzvalene to a ring opening metathesis polymerization in the presence of a non-Lewis acidic tungsten alkylidene metathesis catalyst to form and polybenzvalene. 
     
     
       5. The process of claim 4 wherein said catalyst has the formula (RO) 2  W(N(2,6-diisopropylphenyl))CHC(CH 3 ) 3 , where R=t-butyl or hexafluoro-t-butyl. 
     
     
       6. Product produced by the process of claim 4. 
     
     
       7. A process for forming polypentacyclo-[6.1.1.0 2 .7 0 3 ,5.0 4 ,6 ]undec-9-ene comprising subjecting pentacyclo[6.1.1.0 2 .7 0 3 ,5.0 4 ,6 ]undec-9-ene to a ring opening metathesis polymerization in the presence of a non-Lewis acidic tungsten alkylidene metathesis catalyst to form said polypentacycle-[6.1.1.0 2 .7 0 3 ,5.0 4 ,6 ]undec-9-ene. 
     
     
       8. The process of claim 7 wherein said catalyst has the formula (RO) 2  W(N(2,6-diisopropylphenyl))CHC(CH 3 ) 3 , where R=t-butyl or hexafluoro-t-butyl. 
     
     
       9. Product produced by the process of claim 7. 
     
     
       10. A process for forming polyacetylene comprising: (a) subjecting a monomer to a ring opening metathesis polymerization in the presence of a non-Lewis acidic tungsten alkylidene metathesis catalyst to form a high energy polymer, wherein said monomer and said polymer are selected from the group consisting of ##STR10##   where R is an alkyl and n ranges from about 8 to 7,700; and (b) converting said high energy polymer to said polyacetylene in the presence of a catalyst.   
     
     
       11. The process of claim 10 wherein said metathesis catalyst has the formula (RO) 2  W(N(2,6-diisopropylphenyl))CHC)CH 3 ) 3 , where R=t-butyl or hexafluoro-t-butyl. 
     
     
       12. The process of claim 10 wherein said high energy polymer is isomerized to form said polyacetylene in the presence of a catalyst selected from the group consisting of HgCl 2 , HgBr 2 , Ag +  salts, ZnCl 2 , ZnBr 2 , ZnI 2 . 
     
     
       13. A process for forming polyacetylene comprising: (a) subjecting a benzvalene to a ring opening metathesis polymerization in the presence of a non-Lewis acidic tungsten alkylidene metathesis catalyst to form polybenzvale; and   (b) converting said polybenzvalene to said polyacetylene in the presence of a catalyst.   
     
     
       14. The process of claim 13 wherein said metathesis catalyst has the formula (RO) 2  W(N(2,6-diisopropylphenyl))CHC(CH 3 ) 3 , where R=t-butyl or hexafluoro-t-butyl. 
     
     
       15. The process of claim 13 wherein said polybenzvalene is isomerized to form said polyacetylene in the presence of a catalyst selected from the group consisting of HgCl 2 , HgBr 2 , Ag +  salts, ZnCl 2 , ZnBr 2 , and ZnI 2 . 
     
     
       16. High energy polymers formed by ring opening metathesuis polymerization of monomers having at least one strained ring, said polymers and monomers having the formulae selected from the group consisting of ##STR11## where R is an alkyl group and n ranges from about 8 to 7,700. 
     
     
       17. Polymerized benzvalene and derivatives having the benzvalene structure, the polymer having the general formula given by ##STR12## where N ranges from about 8 to 7,700. 
     
     
       18. Polymerized pentacyclo[6.1.1.0 2 .7 0 3 ,5.0 4 ,6 ]undec-9-ene and derivatives having the pentacyclo[6.1.1.0 2 .7 0 3 ,5.0 4 ,6 ]undec-9-ene structure, the polymer having the general formula given by ##STR13## where n ranges from about 8 to 7,700.